Concerns over the environmental consequences of burning fossil fuels have led to an increasing use of renewable energy generated from sources such as solar and wind. The intermittent and varied nature of such renewable energy sources, however, has made it difficult to fully integrate these energy sources into existing electrical power grids and distribution networks. A solution to this problem has been to employ large-scale electrical energy storage (EES) systems. These systems are widely considered to be an effective approach to improve the reliability, power quality, and economy of renewable energy derived from solar or wind sources.
In addition to facilitating the integration of renewable wind and solar energy, large scale EES systems also may have the potential to provide additional value to electrical grid management, for example: resource and market services at the bulk power system level, such as frequency regulation, spinning reserves, fast ramping capacity, black start capacity, and alternatives for fossil fuel peaking systems; transmission and delivery support by increasing capability of existing assets and deferring grid upgrade investments; micro-grid support; and peak shaving and power shifting.
Among the most promising large-scale EES technologies are redox flow batteries (RFBs). RFBs are special electrochemical systems that can repeatedly store and convert megawatt-hours (MWhs) of electrical energy to chemical energy and chemical energy back to electrical energy when needed. RFBs are well-suited for energy storage because of their ability to tolerate fluctuating power supplies, bear repetitive charge/discharge cycles at maximum rates, initiate charge/discharge cycling at any state of charge, design energy storage capacity and power for a given system independently, deliver long cycle life, and operate safely without fire hazards inherent in some other designs.
In simplified terms, an RFB electrochemical cell is a device capable of either deriving electrical energy from chemical reactions, or facilitating chemical reactions through the introduction of electrical energy. In general, an electrochemical cell includes two half-cells, each having an electrolyte. The two half-cells may use the same electrolyte, or they may use different electrolytes. With the introduction of electrical energy, species from one half-cell lose electrons (oxidation) to their electrode while species from the other half-cell gain electrons (reduction) from their electrode.
Multiple RFB electrochemical cells electrically connected together in series within a common housing are generally referred to as an electrochemical “stack”. Multiple stacks electrically connected together are generally referred to as a “string”. Multiple stings electrically connected together are generally referred to as a “site”.
A common RFB electrochemical cell configuration includes two opposing electrodes separated by an ion exchange membrane or other separator, and two circulating electrolyte solutions, referred to as the “anolyte” and “catholyte”. The energy conversion between electrical energy and chemical potential occurs instantly at the electrodes when the liquid electrolyte begins to flow through the cells.
To meet industrial demands for efficient, flexible, rugged, compact, and reliable large-scale ESS systems with rapid, scalable, and low-cost deployment, there is a need for improved RFB systems.
This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This summary is not intended to identify key features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
In accordance with one embodiment of the present disclosure, a cell in a redox flow battery is provided. The cell includes a first flow frame for flow of a catholyte, a second flow frame for flow of an anolyte, and a separator between the first flow frame and the second flow frame, wherein the separator has a first side and a second side and an outer perimeter, and a gasket-and-separator assembly including a gasket assembly laminated to the separator, wherein the gasket assembly seals the outer perimeter of the separator on the first side and the second side.
In accordance with another embodiment of the present disclosure, a method of making a cell for a redox flow battery is provided. The method includes laminating a gasket-and-separator assembly including a gasket assembly laminated to the separator, wherein the separator has a first side and a second side and an outer perimeter and wherein the gasket assembly seals the outer perimeter of the separator on the first side and the second side, and disposing the gasket-and-separator assembly between a first flow frame for flow of a catholyte, a second flow frame for flow of an anolyte.
In accordance with another embodiment of the present disclosure, a redox flow battery stack of cells is provided. The stack includes a plurality of adjacent cells, each cell including a first flow frame for flow of a catholyte, a second flow frame for flow of an anolyte, and a separator between the first flow frame and the second flow frame, wherein the separator has a first side and a second side and an outer perimeter, and a gasket-and-separator assembly including a gasket assembly laminated to the separator, wherein the gasket assembly seals the outer perimeter of the separator on the first side and the second side.
In any of the embodiments described herein, the separator may be a membrane or a bipolar plate.
In any of the embodiments described herein, the outer perimeter of the separator may be aligned with the outer perimeter of the gasket assembly.
In any of the embodiments described herein, the outer perimeter of the separator may be embedded within the gasket assembly.
In any of the embodiments described herein, the gasket assembly may include a first gasket and a second gasket.
In any of the embodiments described herein, the first gasket may contact the first side of the separator and the second gasket may contact the second side of the separator.
In any of the embodiments described herein, the gasket-and-separator assembly may be formed by pressing the separator between the first gasket and the second gasket.
In any of the embodiments described herein, the first and second gaskets may have flat inner and outer surfaces.
In any of the embodiments described herein, at least one of the first and second gaskets may have a stepped inner surface.
In any of the embodiments described herein, the step of the stepped inner surface may have substantially the same thickness as the separator.
In any of the embodiments described herein, the step of the stepped inner surface may have substantially ½ the thickness of the membrane.
In any of the embodiments described herein, the gasket assembly may further include a filler portion between the first and second gaskets.
In any of the embodiments described herein, the filler portion may be a plastic film or a third gasket.
In any of the embodiments described herein, the plastic film may be selected from the group consisting of polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), polypropylene (PP), polyvinylidene fluoride (PVDF), polyamide (PA), acrylonitrile butadiene styrene (ABS), polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), and combinations thereof.
In any of the embodiments described herein, the pressing pressure may be in the range of 0.01 to 100 MPa.
In any of the embodiments described herein, the pressing time may be in the range of 0.01 to 1000 minutes.
In any of the embodiments described herein, the material for the gasket assembly may be a rubber material selected from the group consisting of acrylonitrile butadiene styrene (ABS) rubber, fluorine rubber, chloroprene rubber, nitrile butadiene rubber, polyisoprene rubber, natural rubber, butyl rubber, ethylene propylene diene monomer (EPDM) rubber, polybutadiene rubber, acrylic rubber, silicone rubber, and combinations thereof.
In any of the embodiments described herein, the surface of the gasket assembly may be prepared prior to pressing.
The foregoing aspects and many of the attendant advantages of this disclosure will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:
Embodiments of the present disclosure are directed redox flow batteries having cell stacks including cells having gasket-and-separator assemblies. Other embodiments of the present disclosure are directed to cells having gasket-and-separator assemblies. Embodiments of the present disclosure are directed to the assembly of cells and cell stacks including cells having gasket-and-separator assemblies.
Embodiments of the present disclosure are directed to redox flow batteries (RFBs), systems and components thereof, stacks, strings, and sites, as well as methods of operating the same. Referring to
Referring to
In the illustrated embodiment of
As a non-limiting example, in a vanadium flow redox battery (VRB) prior to charging, the initial anolyte solution and catholyte solution each include identical concentrations of V3+ and V4+. Upon charge, the vanadium ions in the anolyte solution are reduced to V2+/V3+ while the vanadium ions in the catholyte solution are oxidized to V4+/V5+.
Referring to the schematic in
In one mode (sometimes referred to as the “charging” mode), power and control elements connected to a power source operate to store electrical energy as chemical potential in the catholyte and anolyte. The power source can be any power source known to generate electrical power, including renewable power sources, such as wind, solar, and hydroelectric. Traditional power sources, such as combustion, can also be used.
In a second (“discharge”) mode of operation, the redox flow battery system 20 is operated to transform chemical potential stored in the catholyte and anolyte into electrical energy that is then discharged on demand by power and control elements that supply an electrical load.
Each electrochemical cell 30 in the system 20 includes a positive electrode, a negative electrode, at least one catholyte channel, at least one anolyte channel, and an ion transfer membrane separating the catholyte channel and the anolyte channel. The ion transfer membrane separates the electrochemical cell into a positive side and a negative side. Selected ions (e.g., H+) are allowed to transport across an ion transfer membrane as part of the electrochemical charge and discharge process. The positive and negative electrodes are configured to cause electrons to flow along an axis normal to the ion transfer membrane during electrochemical cell charge and discharge (see, e.g., line e− in
To obtain high voltage, high power systems, a plurality of single electrochemical cells may be assembled together in series to form a stack of electrochemical cells (referred to herein as a “stack,” a “cell stack,” or an “electrochemical cell stack”), e.g., 30 or 32 in
The ion exchange membrane in each electrochemical cell prevents crossover of the active materials between the positive and negative electrolytes while supporting ion transport to complete the circuit. Ion exchange membrane material, in a non-limiting example, a perfluorinated membrane such as NAFION or GORE-SELECT, may be used in the electrochemical cells. Ion exchange through the membrane ideally prevents the transport of active materials between the anolyte and catholyte.
As noted above, a string 10 is a building block for a multiple MW site. As seen in the exemplary layouts in
As a non-limiting example, an exemplary VRB may have capacity up to 125 kW for four hours (500 kW-hours) and a storage string may have capacity up to 500 kW for four hours (2 MW-hours). To be effective as a large scale energy storage system that can be operated to provide multiple layered value streams, individual batteries, designed and manufactured to meet economies of scale, may be assembled as building blocks to form multiple-megawatt sites, for example 5MW, 10MW, 20MW, 50MW, or more. Managing these large installations requires multi-level control systems, performance monitoring, and implementation of various communications protocols.
Referring to
Described herein are systems and methods of operation designed to improve RFB performance on a battery, string, and site level.
Referring to
Referring to
In addition, each electrochemical cell includes bipolar plates 276 at the ends of the cell 238. The bipolar plates 276 are used as current conductors with the cells 238. In the illustrated embodiment, single bipolar plates 276 are shared between adjacent cells 238. As a non-limiting example, the bipolar plate 276 have a thickness of about 1 mm.
Referring to
Sealing structures 282 and 284, such as gaskets, can be used to prevent leakage from the flow frames 272 and 274 for the catholyte and anolyte flow fields 260 and 262. In accordance with embodiments of the present disclosure, the gaskets 282 and 284 can be pre-assembled with a separator, which may be a membrane 270 or a bipolar plate 276, as a gasket-and-separator assembly 290 (see
In previously designed cells, discrete gaskets are placed to sandwich the membranes 270 and the bipolar plates 276 in the cell stack 230 to prevent internal and external leakage of electrolyte. When assembling a cell stack 230, all components must be aligned precisely to ensure a good seal and to achieve adequate electrolyte flow through the surface area of membrane. However, quality control for mass production of cell stacks 230 can be difficult when each component is independently placed in the cell. Misalignment of the battery cell stack 230 can cause electrolyte leakage and/or material corrosion, battery short out, and further damage to the battery system's long term stability and lifespan. When misalignment occurs, the stack has to be disassembled and reassembled. In most cases, it is not possible to reuse all the components of the stack, resulting in membrane waste.
In addition to manufacturing issues, the membrane is expensive material. Therefore, area of the membrane covered by the gasket is not used for ionic exchange and is wasted material.
Embodiments of the present disclosure are directed to manufacturing improvements for the cell stack, improved leakage prevention in the cell stack, improved efficiency in the use of membrane material, and strengthened protection for the membrane edge.
Referring to
In embodiments of the present disclosure, the gasket material for the gasket assembly may be a rubber material selected from the group consisting of acrylonitrile butadiene styrene (ABS) rubber, fluorine rubber, chloroprene rubber, nitrile butadiene rubber, polyisoprene rubber, natural rubber, butyl rubber, ethylene propylene diene monomer (EPDM) rubber, polybutadiene rubber, acrylic rubber, silicone rubber, and combinations thereof.
The membrane may be a cation exchange membrane, an anion exchange membrane, or a porous separator. The membrane may have a thickness in a range of 1 to 300 microns.
In embodiments of the present disclosure, the gasket assembly 392 is laminated to the separator 370 before the cell stack 230 shown in
Prior to assembly, the gasket surfaces can be prepared for assembly. For example, the gasket surfaces can be degreased using volatile solvents including toluene, acetone, methyl ethyl ketone, methyl alcohol, isopropyl alcohol or trichloroethylene, abraded with plastic razor blades or plastic gasket scrapers, and treated using chemical solvents including trichloroethylene solvent, modified bleach solution, or sulfuric acid solution.
In some embodiments, the pressing pressure may be in the range of 0.01 to 100 MPa. In some embodiments, the pressing time may be in the range of 0.01 to 1000 minutes. After lamination, the gasket assembly 392 may be delaminated from the separator 370 without damage to the separator 370 and optionally repressed if one or more gaskets of the gasket assembly needs to be replaced or realigned.
In some embodiments, multiple gasket-and-separator assemblies can be made at the same time in a pressing apparatus by separating the gasket-and-separator assemblies with paper, plastic sheets, metal plates, special fixtures, or by directly using the battery stack hardware.
Referring to
In the embodiment of
In comparison, in the embodiment of
A reduced thickness in the gasket-and-separator assembly 490 may cause, in some cases, alignment problems in the cell stack 230 (see
Referring to
In view of the stepped portion 560, the thickness of the gasket-and-separator assembly 590 is not reduced at the outer perimeter of the first and second gaskets 582 and 584 when pressed. (Compare the embodiment of
Referring to
In view of the stepped portions 660 and 662, the thickness of the gasket-and-separator assembly 690 is not reduced at the outer perimeter of the first and second gaskets 682 and 684 when pressed. (Compare the embodiment of
Referring to
In view of the filler portion 764, the thickness of the gasket-and-separator assembly 790 is not reduced at the outer perimeter of the first and second gaskets 782 and 784 when pressed. (Compare the embodiment of
The filler portion 764 made from a plastic material may be used to reduce cost because the plastic material is less costly than a third gasket (made from gasket material). Suitable plastic film materials may include, but are not limited to, polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), polypropylene (PP), polyvinylidene fluoride (PVDF), polyamide (PA), acrylonitrile butadiene styrene (ABS), polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), and combinations thereof.
When the separator is a bipolar plate, the filler portion 764 may be a third gasket portion 764 sandwiched between the first and second gaskets 782 and 784. Because the bipolar plate is a relatively hard and smooth surface of graphite or metal, the gaskets do not laminate as readily to the bipolar plate as they do to a membrane (which has more surface roughness). The use of three gaskets 782, 784, and 764 allow the gaskets to laminate to each other (having high elasticity and relatively rough surfaces) and the bipolar plate to be lodged in place surrounded by the frame formed by the gasket assembly 792. Likewise, the use of stepping gaskets (as seen in
Because the bipolar plate does not have high elasticity like the membrane, the filler portion 764 gasket can have an increased thickness than the bipolar plate to account for deformation of the filler portion 764 gasket during pressing. For example, in one embodiment, the filler portion 764 gasket has an increased thickness of 0% to 50% than the thickness of the bipolar plate prior to pressing. In another embodiment, the filler portion 764 gasket has an increased thickness of 10% to 30% than the thickness of the bipolar plate prior to pressing. When stepping gaskets are used, such as the stepping gaskets in
Referring to
While illustrative embodiments have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention.
This application claims the benefit of U.S. Provisional Application No. 62/503,852, filed May 9, 2017, the disclosure of which is hereby expressly incorporated by reference herein in its entirety.
Number | Date | Country | |
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62503852 | May 2017 | US |